WO2007122855A1

WO2007122855A1 - Etching solutions, method for regeneration of waste etching solutions and method for the recovery of valuable metals from waste etching solutions

Info

Publication number: WO2007122855A1
Application number: PCT/JP2007/053411
Authority: WO
Inventors: Yasuo Nishimura; Nobuo Kanayama
Original assignee: Tsurumi Soda Co., Ltd.; Toagosei Co., Ltd.
Priority date: 2006-04-25
Filing date: 2007-02-23
Publication date: 2007-11-01
Also published as: CN101432463A; JP5130202B2; TW200741035A; KR20080113059A; JPWO2007122855A1; US20090078679A1; EP2014796A1

Abstract

The invention provides ferric chloride-containing etching solutions for alloy steels such as stainless steel which can be regenerated without removing chromium or nickel and with little increase in the etching solution volume; and a method of etching with the same. An etching solution containing ferric chloride and chromium ions or nickel ions; an etching solution containing ferric chloride, chromium ions, and nickel ions in such amounts that the content ratio among iron ions, chromium ions and nickel ions is nearly equivalent to that of the alloy steel to be etched among the corresponding metals; and a method of etching an alloy steel with an etching solution containing ferric chloride and chromium ions and/or nickel ions in such amounts that the content ratio among iron ions, chromium ions and nickel ions is nearly equivalent to that of the alloy steel to be etched among the corresponding metals.

Description

Etching solution, method for regenerating waste liquid, and method for recovering valuable metals from waste liquid

Technical field

[oooi] The present invention relates to an alloy steel containing chromium and Z or nickel in iron, for example, ferrite

Etching solution for etching austenitic and duplex stainless steels, 36% Ni amber alloy, 42% nickel alloy for lead frames, etc. More specifically, ferric chloride and chromium ions And / or an etching solution containing nickel ions. The present invention also relates to a method for etching alloy steel using this etching solution, a method for regenerating a waste solution of the etching solution (hereinafter referred to as “etching waste solution”), and a method for recovering valuable metals in the power of etching waste solution.

[0002] In recent years, a salty salt having excellent etching properties for metals, such as circuit formation in copper foils of printed wiring boards, removal of burrs generated on punched end faces of metal plates (foil) in electronic component manufacturing, etc. A ferric solution is used. As the alloy steel such as stainless steel is etched using the salty ferric iron solution, as shown in the following reaction formulas (1) to (3), a large amount of chromium and nickel are eluted in the etching solution. In combination with the elution of iron in steel, the etching ability is reduced. When the salt and ferric iron in the etching solution are reduced and the predetermined etching ability cannot be maintained, the etching solution is replaced with a new or regenerated solution, while the used etching solution, ie, the etching waste solution, is replaced. In addition, as shown in the following reaction formulas (4) to (5), after adding an iron material to precipitate and remove chromium and nickel, chlorine oxidation shown in the reaction formula (6) is performed to regenerate the etching waste liquid ( Patent Document 1).

[0003] Metal elution process

3FeCl + Cr → 3FeCl + CrCl (1)

3 2 3

2FeCl + Ni → 2FeCl + NiCl (2)

3 2 2

2FeCl + Fe → 3FeCl (3)

3 2

Metal recovery process

2CrCl + 6H 0 + 3Fe → 2Cr (OH) + 3FeCl + 3H (4) NiCl + Fe → Ni + FeCl (5)

twenty two

Ferric chloride regeneration process (chlorine oxidation)

2FeCl + C1 → 2FeCl (6)

2 2 3

[0004] However, in the method of regenerating the etching waste liquid using the iron material described in Patent Document 1, since the filterability of the precipitated chromium compound is poor, the chromium compound is removed using a polymer flocculant. A method has been devised to generate a floc containing and improve the filterability (Patent Document 2).

[0005] Further, chlorine was blown into an etching waste liquid containing ferric chloride as a main component and further containing ferrous chloride and nickel chloride to oxidize the ferrous chloride in the waste liquid to ferric chloride. After that, the waste liquid without blowing in chlorine is heated and concentrated, and then cooled to 10 to 40 ° C to crystallize and remove salty ferric acid and trace amounts of salty ferrous iron and salty nickel. In this method, the mother liquor with a reduced chloride-packet content is returned to the etching process and recycled (Patent Document 3), and chlorine gas is added to the salted iron etching waste liquid containing nickel to increase the salt content. A method is known in which ferrous iron is oxidized to ferric chloride and concentrated to a specific gravity of 1.6, followed by cooling to crystallize and remove the nickel salt (patent) Reference 4).

[0006] In the method of regenerating a ferric chloride solution from an etching waste solution mainly composed of ferric chloride described in these conventional techniques, it is essential to first remove chromium and nickel. At this time, as shown in the above reaction formulas (4) and (5), the salty ferrous iron is formed, and it remains! / Reacts with the iron material added with ferric chloride (reaction formula (3)) Change to ferrous chloride. In addition, with etching (reaction formula (3)), 1.5 times as much ferrous chloride as ferric salt is generated. For this reason, in the regeneration process in which the salty ferrous iron in the effluent is converted to salty ferric by blowing chlorine, the amount of salty ferric iron increases significantly. The surplus salt 匕 ferric iron had to be discarded. In other words, in the salt and ferric iron business that uses ferric chloride as an etching solution, it was difficult to balance the surplus salt and ferric iron so as to be called the balance business.

Patent Document 1: Japanese Patent Application Laid-Open No. 62-192588

Patent Document 2: Japanese Patent Laid-Open No. 06-127946

Patent Document 3: Japanese Patent Laid-Open No. 09-235684 Patent Document 4: Japanese Patent Laid-Open No. 10-46370

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention provides an etching solution for alloy steels such as stainless steel using salty ferric iron, without increasing the amount of the etching solution without removing the chromium and nickel by covering the iron material. An object of the present invention is to provide an etching solution that can regenerate salt and ferric iron while suppressing the above. It is another object of the present invention to provide a method for etching alloy steel using the etching solution of the present invention, a method for regenerating etching waste liquid, and a method for recovering valuable metals constituting the composition of alloy steel from the etching waste liquid.

Means for solving the problem

[0008] The present invention provides an etching solution containing ferric chloride and chromium ions or nickel ions, and ferric chloride, chromium ions and nickel ions, which meet the above-mentioned purpose. The present invention relates to an etching solution invention. This etching solution contains ferric chloride and chromium ions and / or nickel ions, and may contain each metal ion at a metal composition ratio substantially the same as the metal composition ratio in the alloy steel to be etched. I like it. In addition, this etching solution contains 50 to 30 trivalent iron ions based on ferric chloride based on the total amount of trivalent iron ions based on ferric chloride and chromium ions and Z or nickel ions. 90 weight ^_0/0 and chromium ions or nickel ions etching solution is 10 to 50 weight ^_0/0, Shioi匕第two trivalent iron ions based on iron 50-90 ^_0/0, chromium ions and nickel ions each being at least 7 wt%, and the etching solution total chromium ions and Nikkeruio emissions are 10 to 50 weight ^_0/0, further is preferred etching solution you containing molybdenum ions.

[0009] Further, it is preferable that the etching solution further contains hydrochloric acid.

[0010] The present invention is also a method of etching alloy steel using the above etching solution, or a method of etching alloy steel, wherein the etching solution contains ferric chloride, and the metal in the alloy steel This is an etching method for alloy steel containing each metal ion at a metal composition ratio substantially the same as the composition ratio.

[0011] In this etching method, the etching solution further contains hydrochloric acid. Is preferred.

[0012] The present invention further provides a method for regenerating an etching waste liquid, wherein the salt ferrous iron present in the etching waste liquid is oxidized to the salt ferric iron using chlorine or hydrogen peroxide. A method of etching alloy steel using the regenerated etching solution, a method of recovering valuable metals from the etching waste liquid by collecting the valuable metal by depositing and filtering the valuable metal by adding a neutralizing agent to the etching waste liquid Then, add a neutralizing agent to a part of the etching waste liquid to precipitate and filter the valuable metal, collect the valuable metal and remove ferrous chloride existing in the remainder of the etching waste liquid with chlorine or hydrogen peroxide. It is a method for recovering valuable metals from etching waste liquid and regenerating the etching waste liquid, which is used to acidify salt and ferric acid.

[0013] In the method for regenerating an etching waste solution in which salt or ferric acid is oxidized using chlorine or hydrogen peroxide, it is preferable to further add hydrochloric acid. Further, in the method of recovering valuable metals from the etching waste liquid and regenerating the etching waste liquid, it is preferable to further add hydrochloric acid to the etching solution after oxidizing the remainder of the etching solution waste and the remaining Z or waste liquid.

The invention's effect

[0014] The present invention is an etching solution containing ferric chloride and chromium ions or nickel ions, and an etching solution containing ferric chloride, chromium ions and nickel ions, An etching solution using a salty ferric aqueous solution containing each metal ion at a metal composition ratio substantially the same as the metal composition ratio of the alloy steel to be etched. Etching the alloy steel using such an etching solution has the following advantages over conventional etching solutions containing only ferric salt and ferric iron.

[0015] (1) After iron materials are added to the etching waste liquid to remove heavy metals such as chromium and nickel, salty ferrous iron is converted to salty and ferric iron using chlorine gas and hydrogen peroxide. In the conventional regenerating process to oxidize, the amount of regenerated etching solution increased significantly, and it was necessary to discard the increase.

1S In the present invention, since the heavy metal removal treatment with iron material is unnecessary, the amount of the etching solution does not increase significantly and no waste is generated.

(2) The recycling of the etching waste liquid of the present invention involves only the step of oxidizing ferrous chloride with salt or ferric chloride using chlorine or hydrogen peroxide and the step of adjusting the concentration. Therefore, it is easy to recycle.

(3) The composition specific force of metal ions contained in the etching solution or etching waste liquid Since it is almost the same as the composition ratio of alloy steel, it is possible to recycle heavy metals present in the waste liquid as a valuable metal for alloy steel. it can.

(4) When hydrochloric acid is further added to the etching solution, the removal efficiency of the surface film such as a passive film is good, so the etching performance is good, and insolubles such as iron hydroxide are generated during etching. Can be suppressed.

Brief Description of Drawings

[0016] FIG. 1 is a diagram showing the influence of etching temperature and spray pressure on the etching rate when the etching solutions of the prior art and the present invention are used.

[Fig.2] When alloy steel (SUS316 in this case) is etched using the etching solution of the present invention, valuable metals are recovered from a part of the etching waste liquid, and the remaining liquid is chlorinated to regenerate the waste liquid. It is a figure which illustrates the mass balance of a process.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] The present invention is an etching solution containing ferric chloride and chromium ions or nickel ions, and an etching solution containing ferric chloride, chromium ions and nickel ions. specifically, the trivalent iron ions based on ferric chloride, also chromium ions and Z Te based, to the total amount of nickel ions, iron ions 50-90 ^_0/0 and Kuromuio down or nickel etchant ion is 10 to 50 wt%, iron ions 50-90 ^_0/0, chromium ions and nickel ions are each at least 7 wt%, and the total of chromium ions and nickel ions are 10 to 50 an etching solution by weight ^_0/0. That is, in the present invention, the alloy steel is etched using a salty ferric aqueous solution containing each metal ion having a metal composition ratio substantially the same as the metal composition ratio of the alloy steel to be etched.

[0018] In the present invention, "etching" means melting a non-circuit portion of alloy steel according to a circuit pattern, melting burrs on the punched end surface of alloy steel, or corroding the surface of alloy steel, etc. including.

The “etching solution” in the present invention refers to a state of a new solution containing ferric chloride and chromium ions and / or nickel ions, or a salty ferrous salt in an etching waste solution. Alternatively, it refers to a solution regenerated by acidification with hydrogen peroxide. This is because the etching solution of the present invention elutes iron, chromium, nickel, etc. into the solution as the alloy steel is etched, while the salty ferric iron is reduced to the salty ferrous iron. The metal concentration in the solution changes over time with etching. For this reason, the composition of the etching solution is defined by a new solution or a state after regeneration. Therefore, when the alloy steel is etched using a conventional etching solution containing only ferric chloride, ferrous chloride, ferrous chloride as a result of elution of chromium, nickel, etc. from the alloy steel. Different from solutions containing iron, chromium ions and Z or nickel ions.

[0020] Also, the "etching solution waste" or "etching waste solution" in the present invention means that the alloy steel is etched and the etching solution cannot maintain a predetermined etching capability, and is replaced with a new or regenerated etching solution. This means the used etching solution. It is preferable that almost all of the ferrous chloride in the etching waste liquid is oxidized to salt and ferric acid in the etching solution regenerated from the etching waste liquid. However, the etching solution does not affect the etching capability, that is, the etching solution. It may be a regenerative etching solution in which a small amount of ferrous chloride-iron remains with a ferrous chloride content of 5% by weight or less, preferably 3% or less, more preferably 1% or less. This is because if the ferrous chloride content in the regenerated etching solution is 5% or less, there is no concern that the etching ability will decrease.

[0021] "Alloy steel" etched with the etching solution of the present invention refers to Cr alloys, such as ferritic and martensitic stainless steels, Cr-Ni alloys, such as austenitic and duplex stainless steels. Steel and alloy steels such as Ni alloys such as 36Ni amber alloy and 42Ni alloy for lead frames. That is, it is an alloy steel containing up to about 30% by weight of Cr and up to about 45% by weight of Ni. In addition, in order to meet the required values in the intended use, alloy steels may contain trace elements such as metal elements such as Cu, Mo and Co and Nb, V and Ti in some cases. Typical examples include stainless steels such as SUS430, SUS304, SUS316, etc. stipulated by Japanese Industrial Standards (CFIS), and 42% Ni alloy for lead frames.

[0022] "Valuable metal" in the present invention refers to a metal that is present in an etching waste liquid and is a raw material for recoverable alloy steel, that is, chromium, nickel, molybdenum and the like. [0023] A new solution of the etching solution of the present invention is prepared by dissolving ferric chloride and salt-chromium and / or salt-nickel in an aqueous ferric chloride solution. More preferably, it is an aqueous solution containing each metal ion at almost the same composition ratio as the alloy steel to be etched. The basic salty ferric etching solution preferably contains 18-55 wt% of salty ferric iron in the aqueous solution. If the content is less than 18% by weight, the highly etchable salt and ferric iron content is reduced, the etching ability is lowered, and the etching rate is out of the practical range. On the other hand, if the content exceeds 55% by weight, the viscosity of the etching solution increases, so that the etching solution needs to be heated, and the workability of the etching operation is reduced.

[0024] It should be noted that the etching solution force "contains each metal ion in a metal composition ratio substantially the same as the metal composition ratio in alloy steel" means the composition specific force of iron ions, chromium ions, nickel ions, etc. S, meaning that it is in the range of ± ₃₀ %, preferably in the range of ± 20%, more preferably in the range of ± 10% with respect to the content of each metal in the alloy steel.

Hereinafter, the composition of the etching solution of the present invention will be described. Here, unless otherwise specified, the weight% of each composition is based on the total amount of trivalent iron ions based on ferric chloride, chromium ions, and Z or nickel ions in the etching solution.

[0026] An etching solution of the present invention is a solution containing trivalent iron ions based on ferric chloride, chromium ions, and Z or nickel ions. 90 wt% and chromium ions 10-50 weight ^_0/0 etching solution containing, (2) trivalent iron ions 50-90% by weight and - etching solution containing 10 to 50 wt% of Kkeruion, (3) trivalent iron ions 50 to 90 weight ^_0/0, the chromium ions and nickel ions, each with at least 7 wt%, and an etching solution containing 10 to 50 wt% in total. The etching solution of the present invention is basically a salty ferric solution containing each metal ion at a metal composition ratio substantially the same as the metal composition ratio of the alloy steel to be etched.

[0027] Therefore, it is preferable to properly use the composition of the etching solution according to the composition of the alloy steel as the material to be etched. This is because the ratio of ferric chloride, chromium ions, and nickel ions is always constant when each component of alloy steel is eluted by etching, and the etching solution with the same composition is always supplied when the etching solution is recycled. That is, the ability to easily create an etching solution with the same etching ability. The In addition, since the neutralized product of the etching waste liquid has almost the same metal composition ratio as the alloy steel to be etched, it can be reused as a raw material for alloy steel, and there is a merit that no waste is generated.

[0028] Therefore, when etching Cr-based alloy is a ferritic stainless steel and martensitic stainless steels, trivalent iron ions are 50-90 ^_0/0, the chromium ion is 10 to 50 wt% is preferred etching solution instrument trivalent iron ions 60 to 90 wt%, black ion more preferably etching solution is 10 to 40 weight ^_0/0. Further, 36 Ni Invar alloy, when etching the lead frame for 42Ni alloy, trivalent iron ions 50-9 0 weight ^_0/0, the etching solution is preferably fixture trivalent nickel ion 10 to 50 wt% An etching solution having 50 to 70% by weight of iron ions and 30 to 50% by weight of nickel ions is preferable. On the other hand, when etching a Cr-Ni alloy typified by austenitic stainless steel or duplex stainless steel, trivalent iron ions are 50 to 90% by weight, and chromium ions and nickel ions are each at least 7% by weight. each Tsu Keruion and total etching solution preferably fixture trivalent iron I O emissions from 10 to 50 wt% of 50 to 75 weight ^_0/0, chromium ions and nickel ions -, and the and the chromium ions at least 8 wt ^_0/0 der is, and the etching solvent solution total chromium ions and nickel ions is 25 to 50 weight ^_0/0 is more preferable. Furthermore, in stainless steel containing molybdenum, such as SUS316, an etching solution containing molybdenum ions is preferred.

[0029] However, even if the metal composition ratio of the alloy steel to be etched and the metal composition ratio of the etching solution are not substantially the same, that is, ± 30% with respect to the content of each thread and component metal of the alloy steel. Even if it exceeds this range, there is no particular problem in terms of etching performance. This is because chromium and nickel in the etching composition have no particular effect on the etching performance! /, And even if an etching solution having a slightly different composition ratio is used, each component of the alloy steel This is because the ratio of trivalent iron ions, chromium ions, and-nickel ions approaches the composition ratio of the alloy steel during use due to elution by etching.

[0030] The etching solution of the present invention preferably further contains hydrochloric acid. When the etching solution contains hydrochloric acid, the removal efficiency of the surface film such as the passive film is good, so the generation of insolubles such as hydroxide and pig iron is suppressed during etching with good etching performance. It is because it can do. The content of hydrochloric acid in the etching solution containing ferric salt or ferric salt is preferably 10% by weight or less, more preferably 1 to 5% by weight, based on the weight of the etching solution. .

[0031] The present invention also relates to a method for etching alloy steel, and the etching solution is the same as the method of using the etching solution of the present invention described above, and the etching solution strength is substantially the same as the metal composition ratio in the alloy steel. In this etching method, a salty ferric solution containing metal ions in a composition ratio is used.

[0032] In the present invention, the alloy steel is etched using a ferric chloride solution containing chromium ions and / or nickel ions. That is, the etching solution of the present invention initially contains chromium ions and / or nickel ions that do not affect the etching rate.

[0033] Fig. 1 shows an etching solution of Example la described later containing chromium ions and nickel ions of the present invention, and a conventional etching solution containing only ferric chloride (40-degree Baume product). It is the figure which also compared the viewpoint power of the etching rate. Here, the test was conducted by a spray spray etching method using a small etching test apparatus having a chemical amount of 10 kg. Spraying was performed using a full cone type spray nozzle from 11 cm above the material to be etched. The material to be etched was a 40 mm x 80 mm SUS 316L plate with a thickness of 1 mm. The entire back surface and both ends of the etched surface (5 mm each) were masked, and etching was performed with an effective etching area of 40 mm x 70 mm. The etching rate was expressed as a relative rate with the etching rate obtained by weight reduction at ferric chloride solution temperature: 40 ° C, spray pressure: 0. IMPa as 100.

[0034] The etching rate of the etching solution of the present invention containing hydrochloric acid was also measured by the same method. As a result, it became clear that the etching solutions of the present invention differing only in the presence or absence of hydrochloric acid had almost the same etching rate.

As shown in FIG. 1, when the etching temperature and the spray pressure of the etching solution (spray pressure) are the same, the etching performance of the etching solution of the present invention contains only ferric chloride. It is less than the conventional etching solution. That is, the condition force for using the etching solution of the present invention at 50 ° C. The condition for using the conventional etching solution at 35 ° C. Is almost equivalent to Therefore, it is necessary to set the conditions under which etching is promoted in order that the etching solution of the present invention provides etching performance equivalent to that of the conventional etching solution. Even in the case where the etching solution of the present invention contains hydrochloric acid, it is necessary to set conditions under which etching is promoted in order to obtain etching performance equivalent to that of a conventional etching solution.

[0036] The present invention also regenerates ferrous chloride present in the etching waste liquid after etching the alloy steel using the above etching solution into ferric chloride using chlorine or hydrogen peroxide. The present invention relates to a method for regenerating an etching solution.

[0037] As shown in the above formula (6), the etching solution is regenerated by blowing chlorine gas into the etching waste liquid, oxidizing ferrous chloride in the etching waste liquid to ferric chloride, and then ferric chloride. The concentration can be adjusted to be regenerated as an etching solution. Alternatively, as shown in the following equation (7), ferrous chloride in the etching waste solution is oxidized to ferric chloride with hydrogen peroxide and hydrochloric acid, and then the concentration of ferric chloride is adjusted to perform etching. Can be regenerated as a solution.

2FeCl + H O + 2HCl → 2FeCl + 2H O (7)

2 2 2 3 2

[0038] Upon regeneration of the etching solution, it is preferable to add hydrochloric acid to the waste liquid or the etching solution. Hydrochloric acid can be added before or after Z and ferrous acid are fermented to salt and ferric acid. Since the concentration of the etching solution can be easily adjusted, hydrochloric acid is added to the etching solution after the salt and ferrous acid are oxidized to the salt and ferric acid. It is preferable to do so.

[0039] The present invention also adds a neutralizing agent to the etching waste liquid after etching the alloy steel using the above etching solution to precipitate a valuable metal, and collects the valuable metal by filtration. Etching waste liquid power This invention relates to a method for recovering valuable metals.

[0040] Specifically, the valuable metal is recovered from the etching waste liquid by the following method.

An inorganic base as a neutralizing agent is added to the etching waste solution to precipitate a valent metal such as chromium or nickel, and the precipitate is separated by filtration or centrifugation. The precipitate thus obtained can be used as a raw material for valuable metals such as alloy steel. Inorganic bases as neutralizing agents include alkali metal hydroxides or alkaline earth metal hydroxides. Although it will not specifically limit if it is a thing, Above all, sodium hydroxide sodium or calcium hydroxide calcium is preferable. The pH at which the precipitate is generated is not particularly limited as long as the valuable metal precipitates. Preferably ί or pH 8 to 12, more preferably ί or pH 9 to: L 1.5, particularly preferably ί or pH 9.5 to 11. The precipitate can be obtained by filtration using a general filter paper or by centrifugation using a filter cloth.

[0041] It should be noted that the regeneration of etching waste liquid and the recovery of valuable metals therefrom can be exemplified by the mass balance shown in FIG. That is, 100 kg of etching solution is used to repeat etching of alloy steel (SUS316) to obtain an etching waste solution (102 kg) in which 2 kg of SUS316 is dissolved in the etching solution. Next, 16 kg of the etching waste liquid, which is a part of this etching waste liquid, contains a portion corresponding to the increase due to the etching of 2 kg of SUS316. By neutralizing 16kg of this etching waste liquid, valuable metals such as chromium and nickel can be recovered and used as raw materials for alloy steel and the like. Furthermore, 86 kg of the etching waste solution, which is the remainder of this etching waste solution, is chlorinated to regenerate salt and ferric iron, and water is added to adjust the concentration of salt and ferric iron. Let it play. This regenerated etching solution is equivalent to the etching solution used at the beginning, and can be used for etching SUS316. What is regenerated using 86 kg of etching waste liquid is the force that the content of Fe, Ni, Cr and Mo in the etching waste liquid is the same as that of the etching solution. Fig. 2 illustrates the case where the regenerated etching solution force is 100 kg, which is the same amount as the first etching solution, but the amount of the etching waste liquid for recovering valuable metals and the etching for regenerating the etching solution are shown. The amount of the remaining waste liquid can be appropriately selected as necessary.

[0042] In the illustration of FIG. 2, the addition of hydrochloric acid to the etching waste liquid or the etching solution is performed on the “waste liquid” before oxidizing ferrous chloride to ferric chloride, or Z In addition, it can be added to the etching solution after acidifying the remainder of the waste liquid at the time of “concentration adjustment”. Example

[0043] Hereinafter, the present invention will be described in detail using examples, but the examples are illustrative of the present invention and do not limit the scope of the present invention. In the examples, “% by weight” is a weight ratio based on the weight of the etching solution, unless otherwise specified. [Example la]

Shioi匕第ferric: 24. 6% by weight (8.5 wt% in trivalent iron ions equivalent), nickel ions 1.6 wt ^_0/0 by metallic ions converted from the chloride, chromium ions 2. 3 with wt% and the etching solution 10. OKG containing molybdenum ions 0.28 wt ^_0/0, the temperature 45 ° C, was subjected to etching treatment to the surface of SUS316L spray pressure 0. 15 Mpa. As a result of etching until the concentration of salt and ferric iron in this etching solution reached 9 wt%, 10.2 kg of nickel ions 1.8 wt%, chromium ions 2.8 wt%, molybdenum ions 0 An etching waste solution containing 33% by weight was obtained. Of this 10.2 kg, 8.6 kg is oxidized using about 400 g of chlorine gas, and the concentration is adjusted with water, so that the same composition as the first, ie, 24.6 wt% of salt and ferric iron. An etching solution 10. Okg containing 1.6% by weight of nickel ions, 2.3% by weight of chromium ions and 0.28% by weight of molybdenum ions was obtained. The surplus 1.6 kg was added with water and then neutralized with a neutralizer (32% sodium hydroxide) until the pH reached 11, producing valuable metal precipitates. The recovered metal obtained by filtering this precipitate with a filter paper has a weight metal composition ratio (% by weight) of iron: nickel: chromium: molybdenum = 67: 13: 18: 2, and is to be etched. A neutralized product containing a valence metal having the same weight composition ratio as that of SUS316L was obtained. SUS316L was etched using the etching solution regenerated above.

[0045] In accordance with IS K 1447, the metal components such as iron, chromium, nickel, and molybdenum in the solution are determined to be ICP-AES (inductively coupled plasma emission). Analytical method). The metal weight composition of the recovered material was analyzed by ICP-AES after the recovered material was vacuum-dried to completely remove water, and then redissolved in hydrochloric acid. The recovered material was powdery.

[Example lb]

Shioi匕第ferric: 24. 6% by weight (8.5 wt% in trivalent iron ions equivalent), 2 wt% hydrochloric acid, the nickel ions 1.6 wt ^_0/0 in terms of metal ions from the salt product, Etching solution containing 2.3 wt% chromium ion and 0.28 wt% molybdenum ion 10. Temperature 45 using Okg. The surface of SUS316L was etched at C and spray pressure 0.15 MPa. Etching was performed until the concentration of ferric salt in the etching solution reached 9% by weight. Results, 10. nickel ions 1.8 wt ^_0/0 of 2 kg, chromium ions 2.8 wt ^_0/0, to obtain a waste etching solution containing molybdenum I on 0.33 wt ^_0/0. Of this 10.2 kg, 8.6 kg is oxidized using about 400 g of chlorine gas, and the concentration is adjusted with water and hydrochloric acid, so that 24.6 wt. Etching solution containing 0.1% of hydrochloric acid, 2% by weight of hydrochloric acid, 1.6% by weight of nickel ions, 2.3% by weight of chromium ions and 0.28% by weight of molybdenum ions was obtained. After surplus 1.6 kg is collected, water is neutralized with a neutralizing agent (32% sodium hydroxide) until pH is 11, producing valuable metal precipitates. did. The precipitate valuable metals weight composition ratio of the recovered product obtained by filtration through a filter paper (Weight ^_0/0), iron: nickel: chromium: molybdenum = 67: 14: 18: 2, the A neutralized product containing a valuable metal having a weight composition ratio similar to that of the SUS316L etching material was obtained. SUS316L was etched using the etching solution regenerated above.

[Example 2a]

Etching solution containing 32.6% by weight of ferric salt (11.2% by weight in terms of trivalent iron ions) and 1.5% by weight of chromium ions in terms of metal ions from salty salt 10 Etching was performed on SUS403 using Okg at a temperature of 40 ° C and a spray pressure of 0.1 lOMpa. Until Shioi匕第ferric etching solution of this is 17% by weight, as a result of the etching process, to obtain a waste etching solution containing chromium ions 1.8 wt ^_0/0 10. 2 kg. Of this 10.3 kg, 8.6 kg was subjected to an acid reaction using approximately 400 g of chlorine gas, and the concentration was adjusted with water, so that the same composition as the first, ie, 32.6 wt. % to obtain an etching solution 10. OKG containing chromium ions 1.5 wt ^_0/0. The surplus 1.6 kg was added with water and then neutralized with a neutralizing agent (32% sodium hydroxide) until the pH reached 11 to produce valuable metal precipitates. The recovered metal obtained by filtering this precipitate with a filter paper has a weight metal composition ratio (% by weight) of iron: chromium = 88: 12, which is the same weight as the SUS 403 material to be etched. A neutralized product containing valuable metals having a composition ratio was obtained.

[Example 2b]

32.6% by weight of salty ferric iron (11.2% by weight in terms of trivalent iron ions), 3% by weight of hydrochloric acid, 1.5% by weight of chromium ions in terms of metal ions from salty iron Containing etching solution 1 0. Use Okg! Temperature 40 ° C, Spray pressure 0. lOMpa SUS403 【Etching treatment Was given. As a result of etching until the ferric salt of ferric salt in this etching solution was 17% by weight, an etching waste solution containing 10.2 kg of chromium ions (1.8% by weight) was obtained. Of this 10.3 kg, 8.6 kg was oxidized using about 400 g of chlorine gas, and the concentration was adjusted with water and hydrochloric acid, so that the same yarn was formed, that is, ferric salt. An etching solution 10. Okg containing 32.6% by weight, hydrochloric acid 3% by weight and chromium ions 1.5% by weight was obtained. After surplus 1.6 kg was collected, water was neutralized with a neutralizing agent (sodium hydroxide 32% product) until the pH reached 11 to produce valuable metal precipitates. The recovered metal obtained by filtering this precipitate with filter paper has a weight composition ratio (weight%) of iron: chromium = 88: 12, which is the same weight composition ratio as SUS403 material to be etched. A neutral product containing valuable metals was obtained.

[Example 3a]

Shioi匕第ferric a 19.6 wt% (6.7 wt% in trivalent iron ions equivalent), nickel metallic ions in terms of the chloride ions 2.5 wt ^_0/0, chromium ions 3. the Etsu quenching solution 10. OKG containing 1 wt ^_0/0 Te use!ヽ, temperature 50 ° C, subjected to SUS310S [this E Tsuchingu treated with a spray pressure 0. 2Mpa. Etching treatment until 10% by weight of ferric salt and ferric salt in the etching solution is 10%. Etching waste liquid containing 2.7% by weight of nickel ions and 2.7% by weight of chromium ions. Got. Of this 10.2 kg, 9.2 kg is oxidized using about 300 g of chlorine gas, and the concentration is adjusted with water, so that the same composition as in the beginning, that is, ferric chloride is 19.6 wt. %, Nickel ion 2.5 wt%, chromium ion 3.1 wt% was obtained as an etching solution 10.0 kg. The surplus 1.0 kg was watered and neutralized with a neutralizer (32% sodium hydroxide) until the pH was 11 to produce valuable metal precipitates. The valuable metal weight composition ratio (% by weight) of the recovered material obtained by filtering this precipitate with a filter paper is iron: nickel: chromium = 55:20:25, and the material to be etched is SUS310S. A neutralized product containing valuable metals having a similar weight composition ratio was obtained.

[Example 3b]

Shioi匕第ferric a 19.6 wt% (6.7 wt% in trivalent iron ions equivalent), hydrochloric acid 4 wt%, nickel in terms of metal ions from the chloride ions 2.5 wt ^_0/0, with an etching solution 10. 0 kg containing chromium ions 3.1 wt ^_0/0, the temperature 50 ° C, a spray pressure 0. 2Mpa Etching was applied to SUS310S. Until Shioi匕第ferric etching solution is 9 wt%, as a result of the etching process, containing 10. nickel ions 2.7 wt ^_0/0 of 2 kg, click Romuion 3.4 wt ^_0/0 Etching waste liquid was obtained. Of this 10.2 kg, 9.2 kg was oxidized by using about 300 g of chlorine gas, and the concentration was adjusted with water and hydrochloric acid, so that the same composition as the first, ie ferric chloride, was obtained. wt% hydrochloric acid 4 wt%, Nikkerui on 2.5 wt ^_0/0, to obtain an etching solution 10. OKG containing chromium ions 3.1 wt ^_0/0. The surplus 1. Okg was added with water and then neutralized with a neutralizing agent (32% sodium hydroxide product) until the pH reached 11 to produce valuable metal precipitates. The valuable metal weight composition ratio (% by weight) of the recovered material obtained by filtering this precipitate with a filter paper is iron: nickel: chromium = 55: 20: 25, and the material to be etched is SUS310S. A neutralized product containing valuable metals having a similar weight composition ratio was obtained.

[Example 4]

A neutralized product containing a regenerated etching solution and valuable metals was obtained in the same manner as in Example 1 except that the pH of the neutralization treatment was set to 10.5. Further, SUS316 was etched using the obtained regenerated etching solution. Even if the process of obtaining this regenerated etching solution and the process of etching SUS316 using the regenerated etching solution were repeated, there was no problem in the efficiency of the etching process and the production of neutralized products containing valuable metals. .

[Example 5]

A neutralized product containing a regenerated etching solution and valuable metals was obtained in the same manner as in Example 2 except that the pH of the neutralization treatment was changed to 10.5. Further, SUS403 was etched using the obtained regenerated etching solution. Even if the process of obtaining the regenerated etching solution and the process of performing the etching process using the regenerated etching solution are repeated, the efficiency of the etching process and the production of neutralized products containing valuable metals are not affected. .

[Example 6]

A neutralized product containing a regenerated etching solution and valuable metals was obtained in the same manner as in Example 3 except that the pH of the neutralization treatment was set to 10.5. In addition, SUS310S was etched using the obtained regenerated etching solution. Obtaining this regenerated etching solution; Even when the etching process using the regenerated etching solution was repeated, the efficiency of the etching process and the production of neutralized products containing valuable metals were not hindered.

[Example 7a]

Ferric chloride: 25.9 wt% (8.9 wt% in terms of trivalent iron ions), iron-nickel alloy etching solution containing 5.0 wt% of nickel ions from salt and salt 10 Using Okg, the surface of 36Ni amber alloy was etched at an etching solution temperature of 50 ° C and a spray pressure of 0.2 MPa. As a result of etching until the concentration of ferric chloride and ferric iron in the etching solution reached 11% by weight, an etching waste solution containing 10.3 kg of nickel ions (5.8% by weight) was obtained. 10. Of 3.8 kg, 8.6 kg of acid is reacted with chlorine gas, and the concentration is adjusted with water to make the same yarn as before. That is, 25.9 wt% of salt and ferric iron, nickel ion 5.0 weight ^_0/0 yield the etching solution 10. OKG containing. The surplus 1.7 kg was collected with water and neutralized with a neutralizer (32% sodium hydroxide) until the pH reached 11 to produce valuable metal precipitates. . The collected metal weight composition ratio (% by weight) of the recovered material obtained by filtering this precipitate with filter paper is iron: nickel = 64: 36, which is the same weight composition ratio as the amber alloy of the material to be etched. A neutralized product containing valuable metals was obtained.

[Example 7b]

Ferric chloride: 2'9 wt% (8.9 wt% in terms of trivalent iron ions), hydrochloric acid 1 wt%, nickel ions from chloride 5.0 wt% Solution 10. Okg was used to etch the surface of 36Ni amber alloy at an etching solution temperature of 50 ° C and a spray pressure of 0.2 MPa. As a result of etching until the ferric chloride concentration in the etching solution reached S11 wt%, an etching waste solution containing 10.3 kg of nickel ions 5.8 wt% was obtained. 10. Of the 3 kg, 8.6 kg is oxidized with chlorine gas, and the concentration is adjusted with water and hydrochloric acid to adjust the concentration, that is, 25.9 wt% of ferric chloride and 1 wt% of hydrochloric acid. Then, 10. Okg of an etching solution containing 5.0% by weight of nickel ions was obtained. The excess 1.7 kg was added with water and then neutralized with a neutralizer (32% sodium hydroxide solution) until the pH was 11 to produce valuable metal precipitates. The collected metal weight composition ratio (wt%) of the recovered material obtained by filtering this precipitate with filter paper is iron: nickel = 64: 36, which is the same weight as the amber alloy of the material to be etched. A neutralized product containing valuable metals having a composition ratio was obtained.

Industrial applicability

As described above, with the conventional etching solution, the regeneration solution greatly increases as the waste solution is regenerated, and it is necessary to dispose of the solution. However, in the present invention, heavy metal removal processing is not required for the regeneration of the waste solution. Therefore, recycling of the regenerated solution is not necessary and it is easy to recycle. In addition, the composition specific force of the metal ions contained in the etching solution is almost the same as the composition ratio of the alloy steel to be etched. Therefore, it is possible to recycle heavy metals present in the waste liquid as valuable metal for alloy steel. it can. Since the present invention uses an etching solution that is easy to reduce and recycle waste, it is highly industrially applicable.

Claims

The scope of the claims

[I] It contains ferric chloride and chromium ions or nickel ions, and each metal ion is contained in a metal yarn composition ratio that is substantially the same as the metal yarn composition ratio in the alloy steel to be etched. Etching solution characterized.

[2] An etching solution comprising ferric chloride and chromium ions or nickel ions.

[3] The iron ion force is 0 to 90% by weight and the chromium ion is 10 to 50% by weight based on the total amount of trivalent iron ions and chromium ions based on the salt ferric iron. Or the etching solution of 2.

[4] The iron ion is 50 to 90% by weight and the -Neckel ion is 10 to 50% by weight, based on the total amount of trivalent iron ions and nickel ions based on salt and ferric iron. The etching solution according to 1 or 2.

[5] An etching solution characterized by containing ferric chloride, chromium ions, and nickel ions.

[6] It contains ferric chloride, chromium ions, and nickel ions, and contains each metal ion in a metal yarn composition ratio that is substantially the same as the metal yarn composition ratio in the alloy steel to be etched. Etching solution characterized by.

[7] Based on the total amount of trivalent iron ions based on ferric chloride, chromium ions and nickel ions, 50 to 90% by weight of iron ions and at least 7% of chromium ions and nickel ions each ^_0/0, and, and the total of chromium ions and nickel ions Ru 10-50 wt ^_0/0 der, etching solution of claim 5 or 6, wherein.

[8] The etching solution according to any one of claims 1 to 7, wherein the etching solution further contains molybdenum ions.

[9] The etching solution according to any one of claims 1 to 8, wherein the etching solution further contains hydrochloric acid.

[10] A method for etching alloy steel using the etching solution according to any one of claims 1 to 9.

[II] A method of etching alloy steel, wherein the etching solution contains ferric chloride, Etching method of alloy steel, characterized in that each metal ion is contained at a metal composition ratio substantially the same as the metal composition ratio in one alloy steel.

12. The etching method according to claim 11, wherein the etching solution further contains hydrochloric acid.

[13] The salty ferrous salt present in the waste solution of the etching solution according to any one of claims 1 to 9 is converted into salty ferric acid using chlorine or hydrogen peroxide. How to recycle etching waste liquid.

[14] The waste solution of the etching solution according to any one of claims 1 to 9, wherein a neutralizing agent is added to deposit and filter the valuable metal to recover the valuable metal from the etching waste solution. Collection method.

[15] A neutralizer is added to a portion of the etching solution waste liquid according to any one of claims 1 to 9 to deposit and filter the valuable metal, collect the valuable metal, and remove the etching solution waste liquid. A method of recovering valuable metals from an etching waste liquid and regenerating the etching waste liquid, wherein ferrous chloride existing in the balance is oxidized to ferric chloride using chlorine or hydrogen peroxide.

[16] The recovery of valuable metals and the recovery of etching waste liquid according to claim 15, wherein hydrochloric acid is further added to the etching solution after oxidizing the remaining portion of the etching solution waste solution and Z or the remaining portion of the waste solution. Method.